Preparation of metal derivatives of organic compounds containing a replaceable hydrogen



Patented Sept. 6, 1949 PREPARATION OF METAL DERIVATIVES OF ORGANICCOMPOUNDS CONTAINING ARE- PLACEABLE HYDROGEN John R. Morris,Lawrenceville, 11]., and Joseph E. Fields, Dayton, Ohio, assignors toThe Texas Company, New York, N. Y., a corporation of Delaware NoDrawing. Application April 23, 1947, Serial No. 743,462

This invention relates to the preparation of metal derivatives oforganic compounds containing a replaceable hydrogen by reacting theorganic com ound with an inorganic metal salt in liquid ammonia.

This is a continuation-in-pa t of our. copending applicat on Serial No.480,860 filed March 2'7, 1943, now abandoned.

Among the recent y developed methods of preparing metal derivatives ofor' anic com ounds described in the l terature is the reaction of asolution of a metal in liquid amm n a wi h an organiccompound containinga replaceable hydrogen. The mechanics oi this reaction have not beendefinitely established, but the success thereof is de endent u on thesolubility of the desired metal in liouid ammonia. The a kali andalkaline earth metals are the only me als known to be freely soluble.but certain metals, such as beryllium, zinc, aluminum, gallium,lanthanum, cerium and manganese, although on y slightly solub e, aresufiiciently soluble in liouid ammonia for the purposes of the reaction.Although this reaction has been successfully applied to the preparationof metal derivatives normally difilcult to prepare by the classical metods of synthesis, it possesses certain disadvantages which render ituneconom cal for ada tation to commercial processes. Among thesedisadvantages is the expense involved and the difllculty in handling apure metal. Furthermore, incidental to this reaction, the metallicsolutions react as reducing agents. In the case of organic compoundscontaining some unsaturation in the molecule, this reaction, whileresulting in the metal derivatives, will simultaneously cause areduction of the unsaturated constituents.

According to the present invention a method of preparing metalderivatives of organic compounds containing a replaceable hydrogen hasbeen found which does not result in a reduction of the organic compoundand in which the materials used are more economical and are not asdimcult to handle as in the aforementioned reaction. It has beendiscoveredthat a metal derivative of an organic compound containing areplaceable hydrogen may be obtained by the reaction of an inorganicmetal salt in liquid ammonia. These metal salts may take the form ofhalides, nitrates, metal ammonium halides, metal ammonium sulfates,etc., or any inorganic acid salt which is sufficiently soluble in liquidammonia for the purposes of this reaction. of the various metal saltswhich can be used the 9 Claims. (CL 252-423!) metal halides andparticularly the metal chlorides and metal ammonium chlorides arepreferred.

It is to be understood that whenever the terms "solubility" or solutionof an inorganic metal salt in liquid ammonia, or other terms implyingthe same, are used in the description of the reaction and in the claims,the interpretations given thereto should include that degree ofsolubility necessary for the operation of the reaction.

This reaction may be advantageously carried out in the presence of asolvent substantially immiscible with liquid ammonia. The function ofthis solvent is to remove the reaction product, namely, the metalderivative, from the reaction zone as it is formed. In this manner thereaction goes to completion instead of remaining in a state ofequilibrium due to the hydrolyzing effect of the acids formed in thereaction. In general, the particular solvent used in the reactiondepends upon the type of starting material and the final productexpected. Among the solvents which have been found effective aretoluene, benzene, hexane, xylene, ethyl benzene and ethyl ether.

As previously mentioned, this reaction may be applied to any organiccompound having at least one OH or --SH radical containing a replaceablehydrogen. This category of compounds includes any organic compoundcontaining one or more of the groups:

-OH --COSH -SH CSSH -COOH PSSH such as aromatic or aliphatic alcohols orthicalcohois, aromatic or aliphatic carboxylic acids or thio-carboxylicacids, organic phosphonic acids, and substituted compounds of theforegoing types containing at least one -OH or -SH radical.

The metal salts which have been found to take part in this reaction arethose of the metals falling just above and below hydrogen in theelectromotive series of elements, including tin, lead, iron, antimony,blsmuthand arsenic. The salts of tin, antimony, bismuth and arsenicreact almost quantitatively with excellent recovery of these metalderivatives. The ferric salts appear to react more readily than theferrous salts, although the recovery of the ferric or ferrousderivatives has not been quantitative and in some cases only about halfor less of theoretical. The lead salts appear to be the most difflcultto react, with the yields obtained being still lower.

In the preferred order of reaction a solution of the desired metal saltin liquid ammonia is prepared and to this solution are added smallincrements of a solution of the organic compound in the organic solventimmiscible in liquid ammonia. The reaction mixture is agitated andcontinued in the agitated state for a period after all the organiccompound has been added. The liquid ammonia is then allowed toevaporate. The reaction mass is then filtered and stripped of thesolvent leaving the desired metal derivative.

The following specific examples are given as illustrations of the methodand technique which may be applied to any of the reactions of thepresent invention. The organic compound containing a replaceablehydrogen used in the first three examples, namely, cardanol, is a phenolcontaining an unsaturated allwl group in the meta position. Thiscompound, which is obtained from cashew nut shell oil, is normally veryunstable and subject to polymerization reactions Example I 110 grams(0.55 mol) of anhydrous stannous chloride were dissolved in 2 liters ofliquid ammania and resulted in a greenish yellow solution. The solutionsof the inorganic metal salts in liquid ammonia usually possess acharacteristic color. 300 grams (approximately 1 mol) of cardanol(CaoHszO) were dissolved in 1 liter oftoluene, and the solution addeddrop-wise to the solution of the metallic salt in liquid ammonia whilevigorously stirring. After the addition of all the cardanol, thestirring was continued for two to three hours. The residual ammonia wasallowed to evaporate overnight. Additional toluene was then added, andthe reaction mixture heated, filtered, and the solvent removed bystripping in vacuo. Prior to the removal of the solvent, sufficientmineral lubricating oil was added to produce a 50% by weight concentrateof the final product. The resulting product, namely, the 50% oilconcentrate of the stannous salt of cardanol, analyzed 10.4% SnO:against a theoretical value of 10.8%.

Example II 76 grams 01' antimony chloride were dissolved in 3 liters ofliquid ammonia and a toluene solution of 290 grams of cardanol (CzoHazO)was added. The reaction mixture was vigorously agitated for 8 hours.After standing over night the reaction mixture was heated, filtered,lubricating oil added, and the solvent removed by stripping in vacuo.The resulting 50% oil concentrate of antimony cardanate analyzed 7.9%antimony.

Example III '79 grams of bismuth chloride were dissolved in 2% liters ofliquid ammonia and a toluene solu-'- tion of 290 grams of cardanol(CznlfisO) in 500 ccs. of toluene was added. The reaction mixture wasstirred for 8 hours and, after standing over night, was heated,filtered, lubricating oil added, and the solvent removed by stripping invacuo. The resulting 50% oil concentrate of bismuth cardanate analyzed7.4% bismuth as against a theoretical value 01' 9.8%.

A similar procedure using arsenic chloride gives a comparable yield ofarsenic cardanate.

Example IV 113 grams of SnClz.2H: were heated until anhydrous anddissolved in 2 liters of liquid ammonia. A solution of 275 grams ofdiamyl phenoxy ethanol in 300 cos. of toluene was added slowly withstirring. After standing overnight the reaction mixtures were heated,filtered and stripped of solvent. The resulting stannous diamyl phenoxyethylate analyzed 15.4% 81102.

Example-V 10 grams oi anhydrous stannous chloride were dissolved in 1liter of liquid ammonia and a solution of 50 grams of diamylphenoxyethylsalicylate in 150 ccs. of toluene was added while stirring. The stirringwas maintained for three hours after which the ammonia was allowed toevaporate overnight without stirring. Thereafter 500 ccs. of toluenewere added and the reaction product was filtered. The solvent wasstripped of! under vacuum and lubricating oil added to the reactionproduct. The resulting 50% oil concentrate of the tin salt ofdiamylphenoxyethyl salicylate possessing the following formula analyzed6.7% tin.

Example VI 18.9 grams of anhydrous stannous chloride were dissolved in 1liter of liquid ammonia and a solution of grams of diamylphenoxyethylthiosaiycylate in toluene was added while stirring. The stirring wasmaintained for three hours; afterwards the ammonia was allowed toevaporate over, night. Thereafter additional toluene was added and thereaction product filtered and stripped of solvent. The reaction product,which weighed 66 grams, was then dissolved in 66 grams of 300 pale oilto give a 50% concentrate which analyzed 7.2% tin.

Examp e VII wherein R represents the alkyl aryl nucleus, and RSH theresulting alkyl thiophenol. This material was a viscous liquid whichwould not distill at a temperature of 300 C. under 1 mm. absolutepressure.

The tin salt of this alkyl thiophenol was then prepared in the followingmanner. 60 grams of anhydrous stannous chloride were dissolved in threeliters of liquid ammonia, and a solution of 375 grams of theaforementioned alkyl thiophenol dissolved in 500 cc. of toluene, wasadded in less than one hour with stirring. 200 cc. more toluene wereadded, and the mixture was then stirred for two hours, after which theammonia was evaporated overnight. The reaction mixture was illsome:prepared by the conventional alkali metal-alcohol-metal halide method,apparently due to oxidation to disulfides. Since oxidizing conditionswere entirely absent in the foregoing method of preparation, the desiredtin salt was obtained in satisfactory yield.

Example VIII A high molecular weight C13-C14 alkyl mercaptan having aboiling range of 205-260 F. at 1 mm. absolute pressure and analyzing16.1% by weight of sulphur was converted to the alkyl tin mercaptide inthe following manner. 50 grams of anhydrous stannous chloride were mixedwith 500 cc. liquid ammonia. A mixture of 85 grams of the said alkylmercaptan in 200 cc. of toluene was added in one-half hour withstirring, and

' agitation was continued for 2 /2 hours. The ammonia was then allowedto evaporate overnight, and the reaction mixture filtered and filtercake washed with toluene. The solvent was then removed from the filtrateby distillation at reduced pressure. 107 grams of the alkyl tinmercaptide were obtained, the product being a yellow opaque viscousmass, which became gelatinous on cooling, having an ash content of 29.4%by weight, equivalent to a tin content of 19.1%.

Here again, the tin salt of the alkyl mercaptan could not be prepared bythe conventional alkali metal-alcohol-metal halide method due tooxidation to disulfides.

Example IX An alkyl phenol was prepared by alkylating a butylene polymergasoline fraction having a boiling range of 362-439 F. with phenol inthe presence of anhydrous aluminum chloride catalyst.

The resulting over-all product had a boiling range of 130-230" C. at 1mm. absolute pressure, an average molecular weight of 320, a hydroxylnumber of 129 and a density of 0.939.

The lead salt of the said alkyl phenol was prepared in the followingmanner. 17 rams of lead nitrate were dissolved in 1000 cc. of liquidammonia. 45 grams of the said alkyl phenol dissolved in 100 cc. oftoluene were added dropwise with stirring over a period of 20 minutes,and agitation was continued for three hours. The ammonia was evaporatedby overnight standing without agitation, the reaction product filteredand the solvent stripped from the filtrate. 42.5 grams of a liquidproduct analyzing 1.23% by weight of lead were obtained.

Example X 11.5 grams of ferric ammonium chloride calculated asFezCle-4NH4Cl-2HzO were dissolved in 600 cc. of liquid ammonia. 27 gramsof the alkyl phenol employed in Example IX dissolved in 100 cc. oftoluene were added with stirring over a period of twenty minutes.Stirring was continued for three hours and then the ammonia wasevaporated on standing overnight. The residue was diluted with 100 cc.of toluene, triturated in a mortar and filtered. Following stripping ofthe solvent from the filtrate, 25 grams of a liquid product comprisingthe ferric salt of the alkyl phenol and analyzing 1.49% by weight ofiron was obtained.

A similar run was made employing ferrous am- .monium sulfate in place ofthe ferric ammonium chloride, but in this case a smaller yield of theferrous salt of the alkyl phenol was secured.

Obviously, many modifications and variations of the invention, ashereinbefore set forth, may

be made without departing from'the spirit and scope thereof, but onlysuch limitations should be imposed as are indicated in the appendedclaims.

We claim: 1. A method of preparing a metal derivative of an organiccompoundwhich comprises reacting a solution in an organic solvent of anorganic compound containing at least one radical selected from the groupconsisting of -OH and -SH with a solution of an inorganic metal salt inliquid ammonia, said inorganic metal salt being selected from the groupconsisting of the salts of tin, lead, iron, antimony, bismuth andarsenic which are soluble in liquid ammonia, said organic solvent beingimmiscible with liquid ammonia, and the resultant metal derivative ofthe organic compound being preferentially soluble in said organicsolvent and recoverable as a solution in said solvent.

2. A method of preparing metal derivatives of organic compounds whichcomprises reacting an organic compound containing at least one hydroxylradical, which compounds are inert to liquid ammonia, with a solution ofan inorganic metal salt in liquid ammonia, said inorganic metal saltbeing selected from the group consisting of the salts of tin, lead,iron, antimony, bismuth and arsenic which are soluble in liquid ammonia,in the presence of.an organic solvent immiscible with said liquidammonia and capable of dissolving the metal derivative reaction product,evapo rating the liquid ammonia, filtering the resulting solution ofmetal derivative of the organic compound in the organic solvent, andstripping ofi the organic solvent.

3. A method of preparing metal derivatives of organic compounds whichcomprises reacting an organic compound containing at least onesulfhydryl radical, which compounds are inert to liquid ammonia, with asolution of an inorganic metal salt in liquid ammonia, said metal saltbeing selected from the group consisting of the inorganic salts of tin,lead, iron, antimony, bismuth and arsenic, which are soluble in liquidammonia, in the presence of an organic solvent immiscible with saidliquid ammonia and capable of dissolving the metal derivative reactionproduct, evaporating the liquid ammonia, filtering the resultingsolution of metal derivative of the organic compound in the organicsolvent, and stripping off the organic solvent.

4. A method of preparing metal derivatives of aromatic compounds whichcomprises reacting an aromatic compound containing at least one hydroxylradical with a solution of an inorganic metal salt in liquid ammonia,said inorganic metal salt being selected from the group consisting ofthe salts of tin, lead, iron, antimony, bismuth and arsenic which aresoluble in liquid ammonia.

5. A method of preparing a metal phenate which comprises reacting aphenol with a solution of a metal halide in liquid ammonia, said metalhalide being selected from the group consisting of halides of tin, lead,iron, antimony, bismuth and arsenic, in the presence of an organicsolvent immiscible with said liquid ammonia and capable of dissolvingthe resulting metal phenate.

6. A method of preparing a metal derivative 0! a phenol having analiphatic substituent group, which comprises reacting a solution in anorganic solvent of the phenol having an aliphatic substituent group witha solution of a metal chloride in liquid ammonia, said metal chloridebeing selected from the group consisting of the chlorides of tin, lead,iron, antimony, bismuth 1'0- and arsenic, said organic solvent beingimmiscible with liquid ammonia, and the resultant metal derivative ofthe phenol being preferentially soluble in the organic solvent andrecoverable as a solution in said solvent.

7. The method according to claim 6, wherein the excess liquid ammonia isevaporated from the reaction mixture, the resulting solution of themetal derivative in the organic solvent filtered. and the solventstripped to obtain the metal derivative of the said phenol.

8. The method according to claim 7, wherein a mineral lubricating oil isadded prior to the solvent stripping step to obtain the metal derivativeof the phenol as a concentrate in the mineral lubricating oil.

, a 9. The method according to claim 8, wherein the metal chloride isstannous chloride.

- JOHN R. MORRIS.

JOSEPH 111 FIELDS.

Banana-noes crrrzn The following references are 01' record in the illeof this patent:

I UNITED s'ra'rns PATENTs Number Name Date 1,875,999 Gerlach Sept. 6,1932 mnmcm rn'nm'rs 15 Number Country Date 293,363 Great Britain Julv 2,1928 529,601 Germany July 1'7, 1931 OTHER nnmanncns o Audrieth, Zeit.fur Angew. Chem, vol. 45

